In the recent drive for higher integration and operating speeds in LSI devices, it is desired to miniaturize the pattern rule. Great efforts have been devoted for the development of the micropatterning technology using deep-ultraviolet (deep-UV) or vacuum-ultraviolet (VUV) lithography. The photolithography using KrF excimer laser (wavelength 248 nm) as the light source has already established the main role in the commercial manufacture of semiconductor devices. The lithography using ArF excimer laser (wavelength 193 nm) is under investigation to enable further miniaturization and has reached the stage of prototype manufacture experiments. However, the ArF excimer laser lithography has not matured so that many problems must be overcome before the technology can be applied to an industrial scale of semiconductor manufacture.
The requisite properties for the resist materials to comply with the ArF excimer laser lithography include transparency at wavelength 193 nm and dry etch resistance. Resist materials comprising as a base resin poly(meth)acrylic acid derivatives having bulky acid-labile protective groups as typified by 2-ethyl-2-adamantyl and 2-methyl-2-adamantyl groups were proposed as having both the properties (JP-A 9-73173 and JP-A 9-90637). Since then, a variety of materials have been proposed. Most of them commonly use resins having a highly transparent backbone and a carboxylic acid moiety protected with a bulky tertiary alkyl group.
While these resist materials suffer from several problems, the fluctuation of pattern line width, known as “line edge roughness” (LER), becomes serious in forming finer size patterns. Particularly in the processing of gate electrode zones in the LSI circuit manufacturing process, the LER can cause a fatal defect. It is believed that the LER is affected by various factors. The main factor is the poor affinity of a base resin to a developer, that is, low solubility of a base resin in a developer. Since carboxylic acid protective groups commonly used in the art are bulky tertiary alkyl groups and thus highly hydrophobic, most of them are less soluble. Where a high resolution is required as in the formation of microscopic channels, a noticeable LER can lead to an uneven size, resulting in transistors with degraded electrical properties. One of known approaches for reducing LER is by increasing the amount of photoacid generator added, as described in Journal of Photopolymer Science and Technology, vol. 19, No. 3, 2006, 313-318. Another approach is by rendering more hydrophilic the basic additive for capturing the generated acid, as described in Journal of Photopolymer Science and Technology, vol. 19, No. 3, 2006, 327-334. These approaches, however, exert a less than satisfactory effect.
One of the factors that degrade line edge roughness (LER) is a micro-swelling phenomenon that a resist pattern is swollen as a developer penetrates into the resist pattern. One known approach for anti-swelling is the use of a resin containing a fluoroalcohol partial structure, as described in Journal of Photopolymer Science and Technology, vol. 18, No. 3, 2005, 381-387. The introduction of fluoroalcohol restrains the resin from swelling, but entails the negative effect of facilitating acid diffusion during heat treatment following exposure (i.e., post-exposure baking, PEB). This invites degradation of resolution, failing to gain a satisfactory process window (focal depth, exposure margin, etc.).